Process for insertion of hexafluoropropene at the aliphatic carbon-hydrogen bond of a hydrocarbon or substituted hydrocarbon

ABSTRACT

Process for the addition of hexafluoropropene in the presence of ultra violet light to a hydrocarbon or substituted hydrocarbon compound containing at least one aliphatic carbon-hydrogen bond and which is free of acetylenic and terminal ethylenic unsaturation.

United States Patent 1 Haszeldine et al.

[ PROCESS FOR INSERTION OF HEXAFLUOROPROPENE AT THE ALIPHATICCARBON-HYDROGEN BOND OF A HYDROCARBON OR SUBSTITUTED HYDROCARBON ORSUBSTITUTED HYDROCARBON [76} Inventors: Robert Neville Haszeldine,

Windyridge Lyme Rd., Disley; Ronald Rowland, 6] Bruche Ave. N.. Padgate.both of England [22] Filed: Jan. 5, 1973 [21] Appl. No.: 321,415

301 Foreign Application Priority Data Jan. 24, 1972 Great Britain3328/72 1] 3,816,286 [4 1 June 11, 1974 [52] US. Cl. 204/163 R, 204/162R [51] Int. Cl B0lj 1/10 [58] Field of Search 204/163 R, 162 R [56]References Cited UNITED STATES PATENTS 3,458,4l6 7/1969 Hardwick et al204/163 R Primary Examiner-Benjamin R. Padgett 5 7 ABSTRACT Process forthe addition of hexafluoropropene in the presence of ultra violet lightto a hydrocarbon or substituted hydrocarbon compound containing at leastone aliphatic carbon-hydrogen bond and which is free of acetylenic andterminal ethylenic unsaturation.

3 Claims, No Drawings '1 PROCESS FOR INSERTION OF HEXAFLUOROPROPENE ATTHE ALIPHATIC CARBONJIYDROGEN BOND OF A HYDROCAR'BON OR SUBSTITUTEDHYDROCARBON OR SUBSTITUTED "HYDROCARBON pendant E3) (015347 F i Hgroups; the bracket in the formula being used to indicate that thehydrogen atom may be attached either to the primarycarbon atom, givingrise to a 7 group, or to .the secondarycarbon atom, giving rise togroup.

A variety of methods have been proposed hitherto for the preparation offluorinated organic compounds and compositions. The mainpractical-method has been by the reaction of organic chlorine-containingcompounds with various metallic fluorides thereby to replace thechlorine atom or atoms by fluorine. The particular drawback of thismethod is the cumbersome use of inorganic materials. The method is alsolimited in its applicability. Other methods have involvedelectrochemical fluorination and direction fluorination of organiccompounds, for example, with hydrogen fluoride, fluorine, or certaininorganic fluorides. Again procedures are involved, yields are oftenpoor, and decomposition products of the organic starting material oftenpredominate.

Also known are various telomerisation reactions in which a telogen isreacted with a fluoroolefin to form telomers containing one or morerepeating fluoroolefin units. Such reactions proceed by a free radicalmechanism involving the initial scission of the telogen to form a freeradical, followed by chain propagation and transfer and finally chaintermination, to build up telomers of the type R(fluoroolefln),.X, whereRX is the formula of the telogen. Such processes are disadvantageous inthat it is difficult'to control the value of n in the final product withany degree of precision, the product usually being a mixture ofcompounds having a range of values for n. Although X in-the formula ofthe telogen is usually halogen, the telomerisation reaction has beenextended to telogens where X is hydrogen; see, for example, U.S. PatentSpecifications Nos. 2,411,158, 2,433,844, 2,540,088 and 2,559,628. Suchtelomerisation reactions usually require the presence of a free radicalinitiator, eg a peroxy compound or an azo compound, etc., which may bedisadvantageous in that initiator fragments will appear as contaminantsin the final product.

Yet another technique of introducing fluorine containing groups into anon-fluorinated base material,

particularly polymeric materials, such as polyethylene. polyamides, etc.involves bombarding the base material, whilstinthepresence of afluoroolefin, with high energy particles, e.g. highly acceleratedelectrons or nuclear particles such as protons, neutrons, alphaparticles, deuterons, betaparticles, etc. Such techniques are disclosed,for example, in U.S. Patent Specification No. 3,065,157. The generationof such high energy particles, of course, requires highly sophisticatedexpensive equipment.

'By contrast with the above techniques, we have found that ahexafluoropropene unit can be inserted into an aliphatic carbon-hydrogenbond, i.e., a bond .between a hydrogen atom and a carbon atom which doesnot'form part of an aromatic ring, in a highly controlled manner to givea 1:1 adduct, by a simple photochemical reaction which involves exposingthe compound containing thealiphatic carbon-hydrogen bond to ultraviolet'lightin the presence of hexafluoropropene but in thecompleteabsence of an air or other free oxygen containing gas and in thecomplete absence of any chemical initiator, i.e., free radical formingchemical catalyst.By ,1 :1 adduct we mean the insertion of one and onlyone hexafluoropropene unit into one aliphatic carbon-hydrogen bond inthe molecule, i.e.:

Where the starting compound has more than one aliphatic carbon-hydrogenbond, one molecule of the starting compound may react with two or moremolecules of hexafluoropropene to yield a product having a plurality ofpendant and/or terminal 7 Emil) groups, although, except formacromolecular materials, products having only one insertedhexafluoropropene unit will generally predominate. The process of theinvention is thus quite distinct from a telomerisation procedure-givingrise to terminal groups of the formula CFa) CFzOF H phaticcarbon-hydrogen bond and which is otherwise substantially free of groupsor substituents unstable under the conditions of the reaction. Inparticular, compounds containing terminal ethylenic unsaturation, i.e.groups of the formula CH =CI-I- and CI-I CMeand compounds containingacetylenic unsaturation are to be avoided. The process of the presentinvention is particularly applicable to hydrocarbon starting materialscontaining in their molecular structure at least one aliphaticcarbon-hydrogen bond and which are sub stantially free of acetylenic andterminal ethylenic unsaturation. The reaction is thus applicable toshort and long chain alkanes, e.g. methane, ethane, the propanes,butanes, hexanes, octanes and higher paraffins ranging upwards into oilsand hydrocarbon paraffin waxes; hydrocarbon polymers, including inparticular, polyolefins such as polyethylenes, polypropylenes,ethylenepropylene copolymers, polystyrene; cycloalkanes, e.g.cyclopropane, cyclobutane, cyclopentane, cyclohexane,methylcyclopentane, methycyclohexane, decahydronaphthalene; arylalkanesor alkyl aromatics, such as ethylbenzene, amylbenzene, the xylenes,cymene, trimethylbenzenes; cycloalkenes, such as cyclopentene,cyclohexene, cycloheptene and cyclooctene; and nonterminal alkenes, suchas trimethylethylene, hex-3-ene and but-2-ene.

The insertion reaction of the invention is also applicable to organiccompounds containing functional groups inert under the conditions of thereaction. Such functional groups which may be present in the startingcompounds include, for example, carboxyl, hydroxy, cyanide and ester,ether and thioether linkages, aldehyde, ketone, and sulfur and halogen(e.g. chlorine, fluorine and bromine) atoms.

Typical substituted hydrocarbons usable as starting materials inaccordance with the present invention are carboxylic acids such asacetic acid, propionic acid, isobutyric acid, lauric acid, palmiticacid, stearic acid, toluic acid, phenylacetic acid, adipic acid, sebacicacid, malonic acid, carboxylic acid esters and polyesters withmonohydric and polyhydric alcohols, aldehydes and ketones such asisobutyraldehyde, heptaldehyde, stearaldehyde, acetone, methyl ethylketone, acetophenone, and cyclohexanone; alcohols such as methanol,ethanol, butanol, amyl alcohol, hexanol, heptanol, octanol,cyclohexanol, butan-2-ol, l-phenylethanol, or Z-phenylethanol; etherssuch as dimethyl ether, diethyl ether, dibutyl ether, methyl amyl ether,methyl cyclohexyl ether, anisole, trioxan, dioxan, tetrahydropyran,tetrahydrofuran l,2-dimethoxyethane, methylal, 1,3- dioxalan; alkylsulfides such as dimethyl sulfide, dibutyl sulfide; halogenated andpolyhalogenated compounds including chloroalkanes, fluoroalkanes,chlorofluoroalkanes, bromoalkanes and the like, such as methyl chloride,methylene chloride, chloroform, methyl fluoride, methylene fluoride,chlorodifluoromethane, methyl bromide, ethyl chloride, ethyl fluoride,ethyl bromide, 1, l -difluoroethane, 1,1 l -trifluoroethane, l, l l-trichloroethane, 2,2-dichloropropane, n-propyl chloride, n-propylfluoride, n-hexyl chloride, n-hexyl fluoride, l-chloro-l,l-difluoroethane, l-phenyl- 1 chloroethane; and cyanides such as methylcyanide.

Also included as starting materials in accordance with the presentinvention and in addition to hydrocarbon polymers mentioned earlier aremacromolecular materials such as polyesters, polycarbonates, polyamides,acrylate polymers and copolymers and haloolefin polymers and copolymers.For reasons which will hereinafter become apparent, such hydrocarbon andother macromolecular materials form an especially preferred group ofstarting materials in the insertion'reaction of this invention.

Turning now to the products of the insertion reaction of the presentinvention, and leaving aside for the moment macromolecular startingmaterials, monoinserted products will generally predominate. Dependingon the reactant ratios and on the reaction conditions, however, diandpoly-inserted products can be obtained. I

Generally, it is found that the reactivity of the aliphaticcarbon-hydrogen bond in a hydrocarbon decreases in the series tertiary,secondary, primary. In hydrocarbon starting materials, therefore,insertion of the hexafluoropropene unit will occur at a tertiary carbonatom in preference to a secondary atom, and at a secondary atom inpreference to a primary atom. Thus, in the photochemical reactionbetween n-butane and hexafluoropropene, the major product is C I-ICH(CI-I )CF CFI-ICF (obtained by insertion into a bond between hydrogenand a secondary carbon atom).

In starting materials containing a functional group, the presence of thefunctional group will affect the reactivity of carbon-hydrogen bonds inthe molecule, especially those in the immediate vicinity of thefunctional group or groups. Where a starting material is used whichcontains a functional group no hard and fast rules can be givengoverning the position at which the hexafluoropropene unit is insertedby the reaction of the present invention, except that, in general, theinsertion will occur at the weakest carbon-hydrogen bond. The same istrue of di-insertion products where the introduction of the firsthexafluoropropene group into the molecule introduces a functional groupwhich will influence the position of insertion of second and subsequenthexafluoropropene groups.

As has already been indicated, the hexafluoropropene unit can, intheory, be inserted into the C-H bond in either of two .directions,giving rise either to a straight or branched chain structure in theterminal or pendant group. In practice, it is found that the insertionreaction of the invention usually leads to the formation of the straightchain grouping, i.e., a terminal or pendant group. With certain startingmaterials, however, the isomeric grouping is also obtained.

The insertion reaction of the invention provides a route to a wide rangeof fluorinated organic compounds. Where a hydrocarbon reactant is usedthe product will consist of a hydrocarbon backbone carrying one or morependant and/or terminal groups. Such compounds have a variety of uses.The products are often liquids and oils with a low freezing point and ofgood chemical and thermal stability attributable to the presence offluorocarbon unit or units. These liquids and oils make usefuldielectric liquids,

non-corrosive heat exchange media, solvents, lubricants, etc. Theproducts also form a useful starting point for the preparation of otherfluorinated organic compounds containing functional groups. Inparticular, the presence of the hydrogen atom in the terminal or pendantfluorocarbon group renders the group susceptible to dehydrofluorinationto form a terminal or pendant perfluoroolefin group, e.g. aperfluoroallyl group: -CF CF:CF a perfluoropropenyl group: -CF:CFCF or aC:CFCFHCF group. Such unsaturated groupings open up a route to a widerange of derivatives. More especially, such unsaturated compoundscnstitute a valuable class of fluorocarbon olefins capable of a varietyof chemical reactions, including, in the case of compounds containingthe perfluoroallyl grouping, homoor polymerisation with, for example,other fluoroolefins, such a vinyl or vinylidene fluoride ortetrafluoroethylene, to provide novel fluorocarbon polymers. The routeto such unsaturated compounds is illustrated by the following reactionscheme:

-HF CH5 (EH3 CHzCHKBHCFzCFCFz and/or CHJCHQCSCFCFHCFG, l

a. W. a e 2HF CHaCHzCHzCH; oHioHioH-c Flo FHC F3 U.V.llght 1 Also ofinterest are adducts of hexafluoropropene and aromatic compounds, e.g.of the formula RCH R' where at least one of R and R is an aromaticgroup, the other, when not aromatic, being hydrogen or an aliphatichydrocarbon radical free of acetylenic or terminal ethylenicunsaturation. With such starting compounds, the insertion reaction ofthe invention gives rise of 1:1 adducts of the formula RR'CHCF CFHCFwhich provide a sueful starting point for the synthesis of biologicallyactive compounds.

When using a starting material containing a functional group or groupsthe insertion reaction of the present invention provides a route to awide range of substituted hydrocarbon compounds having as substituentsboth a functional group, e.g. carboxyl, hydroxyl, halogen, cyanide, oran ester or ether linkage, and a fluoroalkyl group. The products areoften liquids and oils with a low freezing point and of good chemicaland thermal stability attributable to the presence of the fluorocarbonunit or units. These liquids and oils make useful dielectric liquids,non-corrosive heat exchange media, solvents, lubricants, etc. Many ofthe products obtainable by the reaction of the present invention, e.g.those obtained from carboxylic acids exhibit useful surface activeproperties. The presence of the functional group renders the productsobtained by the insertion reaction of the present invention particularyvaluable starting materials for the synthesis of other usefulderivatives. For example, the polyfluoroalkanols obtained by inserting ahexafluoropropene unit into an alkanol by the method of this inventionmay be esterified, for example, with acrylic acid, to give fluoroalkylacrylates useful for conversion to products, e.g. polymers, useful fortheir surface active properties and capable of imparting water-proof,crease and stain resistant finishes to textiles. The polyfluoroalkanolsmay also be used to prepare polyfluoroolefins by a dehydration reaction,e.g.

CH zCMeCF CFHCF which are also useful as monomers and comonomers in thepreparation of fluorinated polymers capable of imparting oil and waterrepellant finishes to textiles.

The fluorinated adducts obtained by the present invention can also beused as intermediates in the preparation of agricultural andpharmaceutical chemicals. Adducts obtained by inserting ahexafluoropropene group into an already fluorinated reactant, representnew compounds of potential value as aerosol propellents, refrigerants,anaesthetics and intermediates for the fluoropolymer industry.

As already indicated, the photochemical insertion reaction of theinvention is carried out simply by exposing the reactants to ultraviolet light in the absence of air or other free-oxygen-containing gasand in the absence of any chemical initiator. The reaction may beperformed under an inert atmosphere or in a vessel from which allextraneous material is excluded, for example, by evacuation, followed byvacuum transfer of the reactants into the evacuated vessel. The reactionproceeds satisfactorily in the absence of solvents, but the presence ofan inert solvent is often preferred. Most suitable as inert solvents arehighly halogenated hydrocarbons.

Temperature and pressure are not critical. The reaction proceedssatisfactorily at room temperature, i.e., about 20C, although moderatelyelevated temperatures, e.g. up to about C, may be used. in many casestemperatures in the range of about 30-l00C will be preferred.

The reaction may be carried out under atmospheric pressure. in mostcases, however, superatmospheric pressures in the range of about l-l2atmospheres will be preferred. Where the reactants are suitable, thereaction of the present invention can be carried out under continuousflow conditions.

Reactant ratios are not critical and are largely dependent upon thedegree of insertion desired. A molar excess of hexafluoropropene willfavor the formation of diand poly-insertion products. A molar excess oforganic C-H reactant will favor the formation of mono insertionproducts. For a high yield of the mono insertion products molar ratios(organic reactant: hexafluoropropene) in the range 2:1 to 4:1 arepreferred.

Turning now to macromolecular reactants, an important application of thephotochemical insertion reaction of this invention is in themodification of polymeric materials, in particular, of normally solid,high molecular weight polyolefins, such as polyethylene, polypropylene,polyisobutylene, polyamides, such as nylon, acrylic polymers, such aspolymethyl methacrylate, polyesters, such as Terylene, polyhaloolefinsand polycarbonates. The reaction of the invention may also be applied tothe modification of naturally occurring macromolecular materials e.g.cellulosic materials such as cotton, paper, etc. The insertion ofpendant -(orii i )a groups into the polymer molecules modifies manyimporatnt properties of the polymer, e.g. melt flow properties, surfacecharacteristics and moulding properties, without any appreciablecross-linking of the polymer molecules. This is in considerable contrastto the technique discussed hereinbefore of bombarding the polyt mer inthe presence of the fluoroolefin with high energy particles, whichtechnique, involving as it does, the formation of free radical sites,inevitably results in crosslinking of the polymer. In addition, theinsertion reaction of the present invention may be used to enhance thechemical and thermal stability of the polymer.

The insertion reaction employing macromolecular starting material iscarried out under substantially the same conditions of temperature andpressure discussed above for lower molecular weight compounds. Thereaction of the invention may be used to give a surface treatment topolymers in the massive state: for example, the reaction may be used tomodify the surface properties of polymer beads or moulded articles; aparticular utility of the invention, however, resides in the treatmentof polymeric material in the form of fibres or thin films. Such fibresand films are often temperature sensitive. Nevertheless, such films andfibres can be treated according to the invention at temperatures belowthat at which melting or other physical deformation takes place toprovide fibres and films having substantially modified surfaceproperties.

The amount of hexafluoropropene employed will depend on the degree ofinsertion desired and this in turn will depend on the modificationdesired in the final products. The insertion of as little as 1-12percent by weight of hexafluoropropene units into the polymer iseffective to provide significant changes in melt flow, surfaceproperties and moulding characteristics. Substantially greater changesin the physical and chemical properties of the polymer may be broughtabout by the insertion of higher, e.g. up to 60 percent, ofhexafluoropropene. The precise effects will differ from polymer topolymer. For example, the insertion of 14% by weight ofhexafluoropropene into solid high molecular weight polyethylene convertsthe polymer into a highly fluorinated oil composition highly resistantto oxidative or other chemical degradation and useful as a heat transferfluid or dielectric. The reaction of the present invention isparticularly useful in imparting oil and waterrepellent properties topaper and textile fabrics and also in imparting crease resistance andshrink resistance to fabrics such as wool and cotton.

The invention is illustrated by the following examples:

pene (1.36 g., 11.4 mmole) were sealed in a 300 m1. silica ampoule andirradiated with ultra violet light from a Hanovia (Registered TradeMark) S. 500 lamp placed at a distance of 15 cm. from the ampoule for 24hours. Fractionation of the gaseous products gave hexafluoropropene 1.36g., 9.1 mmole; percent recovery); n-propane (1.13 g., 25.7 mmole; 75percent recovery) and 1,1,1,2,3,3-hexafluoro-4-methylpentane (0.2 g.,1.03 mmole; 45 percent yield based on C F consumed).

EXAMPLE ll Following the procedure of Example 1, isobutane (1.98 g.,34.2 mmole) and hexafluoropropene 1.21 g., l 1.4 mmole) were sealed in asilica ampoule and irradi ated with ultra violet light for a period of24 hours. Fractional separation of the products gave isobutane (1.74 g.,30.0 mmole, 88 percent recovery); hexafluoropropene (1.21 g., 8.1 mmole;71 percent recovery) and 1,1,1 ,2,3,3-hexafluoro-4,4-dimethylpentane(0.36 g., 1.73 mmole; 52 percent yield based on C F consumed).

EXAMPLE 111 Following the procedure of Example I, cyclohexane (5.74 g.,68.4 mmole) and hexafluoropropene (3.42 g., 22.8 mmole) were sealed in asilica ampoule and irradiated, whilst being shaken mechanically, withultra violet light for 24 hours. The gaseous and liquid products wereseparated. The gaseous product was shown to contain hexafluoropropene1.58 g., 10.4 mmole; 46 percent recovery). Fractionation of the liquidproducts gave cyclohexane (4.70 g., 56 mmole; 82% recovery) and1,l,2,3,3,3-hexafluoropropylcyclohexane (2.46 g., 10.5 mmole; 85 percentyield based on C F consumed) b.p. 158l59C (Found: C, 46.3; H, 5.2; F,48.6 percent M (mass spectrometry) 234. C H F requires C, 46.2; H, 5.2;F, 48.6 percent; M 234.

EXAMPLE IV Cyclopentane (4.79 g., 68.4 mmole) and hexafluoropropene(3.42 g., 22.8 mmole) were irradiated in a mechanically shaken silicaampoule with ultra violet light for 60 hours. The gaseous and liquidproducts were separated, the gaseous product containinghexafluoropropene (1.73 g., 11.5 mmole; 50 percent recovery).Fractionation of the liquid gave Cyclopentane (4.13 g., 59.0 mmole; 86percent recovery) and l,1,2,3,3,3- hexafluoropropylcyclopentane (1.85g.,8.41 mmole; 74 percent yield based on C F consumed) b.p. 132C (Found: C,43.9; H, 4.6; F, 51.5 percent; M (mass spectrometry), 220. C H Frequires C, 43.6; H, 4.6, F, 51.8 percent; M, 220).

EXAMPLE V Tetrahydropyran (5.88 g., 68.4 mmole) and hexafluoropropene(3.42 g., 22.8 mmole) were irradiated in a mechanically shaken silicaampoule for 72 hours. Gaseous and liquid products were separated. Thegaseous product contained hexafluoropropene (0.02 g., 0.1 mmole; 0.4percent recovery). Fractionation of the liquid product gavetetrahydropyran (4.22 g., 49.1 mmole; 72. recovery) anda-(1,1,2,3,3,3-hexafluoropropyl) trihydropyran (4.36 g., 18.5 mmole; 82percent yield based on C 1 consumed) b.p. l64-168C. (Found: C,40.6; H,4.5; F, 48.6 percent; M (mass spectrometry), 236. C H F O requires: C,40.7; H, 4.3; F,

48.3 percent; M 236. The a-(1,1,2,3,3,3-hexafluoropropyl) trihydropyranwas resolved by preparative gas liquid chromatography into equimolaramounts of its two diastereoisomers.

cent recovery) and l-chloro-l .1,2.2.3,4,4.4- octafluorobutane (0.046g., 0.2 mmole; 4 percent yield based on C 'F consumed).

EXAMPLE X for 9 days. Separation of the products gave hexafluoropropene(0.95 g., 6.3 mmole; 55 percent recovery), chlorodifluoromethane (2.08g.. 24.0 mmole; 70 per- 5 EXAMPLE VI Ethyl fluoride 1.65 g., 34.4 mmole)and hexafluoro- 1,4-Di0Xan 8- mmole) hexafluofopropropene(1.73 g., 1 1.4mole) were sealed in a silica am- P 8- mmole) were irradiated in a pouleand irradiated with ultra violet light for 44 hours. chanically shakensilica ampoule with ultra V1016! light Separation of the products gavehexafluoropropene for 72 hours. Separation of the gaseous products gave0 (136 g 9,05 mmole; 80 percent recovery), ethyl fluohexafluoropropenegs mmole; 38 percentreride (1.56 g., 32.5 mmole; 95 percent recovery)and covery). Fractionation of the liquid products gave 1,4-1,l,1,2,3.3,4-heptafluoropentane (0.1 g., 0.5 mmole; dioxane (4.70 g.,53.4 mmole; 78 percent recovery) 22 percent yield based on C 1consumed). and 2-( 1,1,2,3,3,3-hexafluoropropyl) l ,4-dioxan (3.21 g.,13.5 mmole; 95 percent based on C F EXAMPLE XI consumed) b.p. l75l77C.(Found: C,35.3;l-l,3.4; F, Samples of polyethylene film 2 inches X 5inches 48.0 percent; M (mass spectrometry), 238. C H F O were placed insilica ampoules. The ampoules were requires: C, 35.3; H, 3.4; F, 47.9; M238 The product then evacuated and charged with hexafluoropropene to2-(1,1,2,3,3,3-hexafluoropropyl)-1,4-dioxan was revarious pressures.Care was taken to exclude air and solved by preparative gas liquidchromatography into moisture during charging. The ampoules were thenequimolar amounts of its two diastereoisomers. sealed and irradiatedwith ultra violet light from a 500 EXAMPLE V" W l-lanovia lamp forperiods of from 7 to 72 hours. As a first control experiment a filmsample was sealed in Butan'z-ol (5-06 8- mmole) and F PQ P an evacuatedsilica ampoule without any hexafluoro- P (3-42 8" mmole) were Sealed m aslllca 25 propene and was kept in the dark for 72 hours without pouleand irradiated with ultra violet light and simultairradiation AS aSecond comm], another fil Sample neously Shake" mechanically for 72hours- Gaseous was sealed in an evacuated silica ampoule without anypX'OdUCtS were shown to contain methane g., hexafluoropropene but wasthen irradiated for mmole), carbon monoxide (0.084 g., 3.0 mmole) and hhexaflu r pr p (0045 g-, mmole; 15 Percent Irradiation was carried outat room temperature, i.e., rec ry)- ctionation of the liquid productsgave no special effort was made to heat or cool the ampoules butan-2-ol(3.09g., 41.7 mmole; 61 percent recovery) during irradiation. Theproximity of the UV lamp, howand4,4,5,6,6,6-hexafluoro-3-methylhexan-3-ol (4.88 ever, caused thetemperature in the ampoules to rise to g., 21.8 mmole; 97 percent yieldbased on C F 40-60 during the course of the irradiation. consumed). b.p.157l58C (Found: C, 37.8; H, 4.6 At the end of the experiment the sampleswere percent. C H, F,,O requires C, 37.5; H, 4.5 percent). analysed forfluorine content and the surface properties investigated by measurementof the contact angle of EXAMPLE ethyl benzoate on the surface andmeasurement of the Methyl fluoride (0.7 g mmole) and hexafluoroangle ofrepose on untreated polyethylene film and on propene 1.54 g., 10.3mmole) were sealed in a silica rubber. The values were compared withthose obtained ampoule and irradiated with ultra violet light for 6 withan untreated polyethylene sample and with the hours. The gaseous andliquid products were separated control samples. to givehexafluoropropene (0.75 g., 5.0 mmole; 49 per- The results are shown inTable I.

TABLE I C F, Period of Sample pressure irradiation Analysis ContactAngle Angle of Repose atmos. hrs. 73F Side A Side B Polyethylene RubberOriginal N11. N11. NIL 16 16 23 32 film Control 2 NIL 72 ML 22 15 22 401 s 72 4.2 53 38 30 56 2 8 7 2.0 55 42 25 53 3 1 72 1.8 35 23 60 4 1 20circa 1 56 23 52 cent recovery), methyl fluoride (0.62 g., 18.2 mmole;The infra red spectra of the treated films shows sig- 88 percentrecovery) and 1,2,2,3,4,4,4-heptanificant C-F absorption at 7.8, 8.45and 9.141., and fl b t ()4 25 l 5 percent i ld changes in thecystallinity of the polymer films were based on C3F6 consumed). 60suggested by alterations in the relative intensities of ab- EXAMPLE IXsorption at 13.75 and 13.9512. Mass spectrographic investigation showedthat adsorption of fluorocarbon was chlorfldifluofomelhane 8- mmole) andnot the cause of the observed changes in the propertieshexafluoropropene (1.71 g., 11.4 mmole) were sealed f the fil in asilica ampoule and irradiated with ultra violet light The change insurface properties of the polyethylene film is shown by the increasedangles of contact of ethyl benzoate and the increase angle of repose onuntreated polyethylene and rubber. The increase of the angle of hancedby moderately elevated temperatures.

l1 l2 repose on rubber, representing a substantial increase in TABLE 11the surface friction is particularly marked.

Investigation of the properties of the polymer film CIR. Period from thefirst control experiment showed that the propgi g RCPM erties of theoriginal film were unchanged. The second 5 Sample illmUS. hours '7 FPolyethylene Rubber control experiment showed that there are nosignificant 0 NlL Nll. NIL 28 30 changes either when the film ISirradiated in the ab- A sence of hexafluoropropene. Sample filmsirradiated in EXAMPLE XVI By the procedures of Example XI, the effect ofthe sertion reaction of the present invention on polypropylene film wasinvestigated. The results are shown in from taking place. Table IV.

TABLE IV C l- Period Prcsof irra- Analsure diation Temp ysis ContactAngle Angle of Repose Sample atmos. hours C F Side A Side B PolyethyleneRubber Original NIL NIL RT" NIL 10 l0 22 53 film Control NIL 72 RT* NIL9 9 53 1 8 72 RT* 0.4 23 20 24 50 2 8 72 85 1.3 53 42 23 57 roomtemperature EXAMPLE XII The experiment of Example XI was repeated exceptthat the silica ampoules were mounted in a silica jacket through which acooling or heating medium was passed silica ampoule. The results areshown in Table II.

The infra red spectra of the treated film show bands at 7.85 and 8.45,u. which are associated with C-F ab- The above results show that thephotochemical insertion of hexafluoropropene into polyethylene is en-EXAMPLE XV Polyethylene terephthalate film (Melinex) samples wereirradiated with ultra violet light in the presence of hexafluoropropeneby the procedures of Example XI.

The results are shown in Table V.

TABLEV C F Period Pres of irra- Analsurc di fl ysis Angle Angle ofRepose Temp Contact Sample atmos. hours C 71 F Side A Side BPolyethylene Rubber Original NIL NIL RT NIL 20 20 30 film Control NIL 72RT NIL 33 32 30 48 l 8 72 RT 0.2 45 25 28 68 2 8 72 1.0 42 38 25 48EXAMPLE XIII EXAMPLE XVI Sample films of Nylon 6 were irradiated withultra violet light whilst in contact with hexafluoropropene by theprocedure of Example XI. The results are shown in Table VI.

TABLE VI C F Period Presof irra- Analsure diation ysis Angle Angle ofRepose p Contact Sample atmos. hours C '71 F Side A Side B PolyethyleneRubber Original film NIL NIL RT NIL 22 22 23 35 Control NIL 72 RT NIL(a) (a) 28 38 1 8 72 RT 0.9 15 45 (a) The treated film was too crinkledto obtain any measurements.

Strong infra red absorption centered on 8.811. was EXAMPLE XX noted inthe infra red spectra of the treated film. The treated films showed anincrease in fraction.

EXAMPLE XVII Sample films of unplasticized P.V.C. were irradiated withultra violet light whilst in the presence of hexafluoropropene by theprocedure of Example XI. The results are shown in-Table VII Samples ofcotton Dacron 1035 were irradiated in the presence of hexafluoropropeneunder the conditions specified in Example XIX. Analysis showed afluorine content of 0.2 percent in the irradiated fabric. The angle ofrepose of the treated samples on untreated Dacron 1035 and rubber were78 and 52 respectively compared with 69 and 47 for untreated cottonDacron.

' TABLE vu qr. Period Presof irra- A l.

s di rin y i A l Angle of Repose Temp. Contact Sample atmos. hours C FSide A Side B Polyethylene Rubber Original NIL NIL RT NIL 32 (a) 27 40film Control NIL 72 RT NIL 31 (a) 32 42 1 8 72 RT 0.2 30 (a) 70 47 (3)No measurement was possible on the reverse side because of a very rapidspread EXAMPLE XVIII Sample films of polystyrene were irradiated withultra violet light whilst in contact with hexafluoropropene by theprocedure of Example XI. The results are shown in Table VIII.Irradiation was carried out at room temperature.

Sample pieces of cotton Twill 423 were irradiated with ultra violetlight in the presence of hexafluoropropene at 8 atmospherer pressure for72 hours by the procedure of Example XI.

Irradiation was carried out over 72 hours at room temperature.

Analysis of the fabric sample at the end of the irradiation showed afluorine content of 2 percent. The angles of repose of the treatedsamples on an untreated piece of cotton twill and on rubber were 85 and60 respectively compared with 78 and 55 respectively for samples of theoriginal untreated twill.

The treated samples were found to be markedly water resistant and wouldfloat on water; they showed no shrinkage on washing.

. The treated samples were waterproof.

EXAMPLE XXI Leather samples (Crust Cowhide Garment Leather) irradiatedwith ultra violet light in the presence of hexafluoropropene under theconditions specified in Example XIX showed angles of repose on untreatedleather and rubber of 39 and 50 compared with 37 and 48 respectively foruntreated control samples. The treated samples took on a rubbery feel.Analysis showed a fluorine content of 1.7 percent.

EXAMPLE XXII Samples of Kraft paper were irradiated with ultra violetlight in the presence of hexafluoropropene (1 atmosphere) for 72 hoursat room temperature.

The angles of repose of treated samples on untreated Kraft paper andrubber were 42 and 55 respectively, compared with 37 and 52 foruntreated control samples.

The treated samples were waterproof and showed an increase in tensilestrength. The breaking weight was 2.44 kg. as against 2.36kg. foruntreated control samples. The fluorine content of the treated sampleswas 1.1 percent.

EXAMPLE XXIII n-Butyl alcohol (26.0 g., 351 mmole) and hexafluoropropene(17.6 g., 117 mmole), sealed in vacuo in a 300 ml. silica ampoule,shaken and irradiated with ultra violet light from a SOO-watt Hanovialamp for 5 days gave (i) hexafluoropropene (9.36 g., 62.4 mmole; 53

EXAMPLES XXIV n-Heptyl alcohol (20.3 g., 175.5 mmole) andhexafluoropropene (8.8 g., 58.5 mmole), sealed in vacuo in a 300-ml.silica ampoule, shaken and irradiated with ultra violet light from 500watt Hanovia lamp for seven days gave, from distillation of the productsfrom two such tubes, hexafluoropropene 10.05 g., 67 mmole; 57 percentrecovery), n-heptanol (34.3 g., 296 mmole; 84 percent recovery), andl,l,1,2,3,3 hexafluoro-4-hydroxydecane. (ca. 12.2 g., 46 mmole; 92percent yield base on hexafluoropropene consumed), b.p 48/0.6 mm. The Fnmr spectrum of 1,1,- l,2,3,3-hexafluoro-4-hydroxydecane indicated thepresence of a pair of diastereoisomers.

EXAMPLE XV n-Octyl alcohol (22.2 g., 171 mmole) and hexafluoropropene(8.55 g., 57 mmole), shaken and irradiated for seven days in silica gavehexafluoropropene (2.2 g., 14,8 mmole; 26 percent recovery), n-octylalcohol (16.3 g., 125.4 mmole; 73 percent recovery), and 1,1,-1,2,3,3-hexafluoro-4-hydroxyundecane (9.8 g., 35 mmole; 83 percent yieldbased on hexafluoropropene consumed), b.p. 93-95/3 mm. The F nmrspectrum of 1,l,1,2,3,3-hexafluoro-4-hydroxyundecane indicated thepresence of a pair of diastereioisomers.

EXAMPLE XXVI Hexafiuoropropene (21.4 g., 14.25 mmole) andtetrahydrofuran (2.64 g., 36.67 mmole), sealed in vacuo in a silica tube(ca. 10 ml) and irradiated with ultra violet light for 100 hours gavetetrahydrofuran (1.55 g. 21.53 mmole), anda-(1,l,l,2,3,3-hexafluoropropyl)- trihydrofuran (2.90 g., 13.06 mmole;92 percent yield based on hexafluoropropene consumed (Found: C, 38.8; H,4.0. C H F O requires C, 37.8; H, 3.6 percent, b.p. l37-8.

EXAMPLE XXVII Hexafiuoropropene (2.44 g., 16.27 mmole) and dimethylether(1.92 g., 41.74 mmole) sealed in vacuo in a silica tube (ca 10 ml), andirradiated with ultra violet light for 95 hours gave dimethylether (0.86g., 18.69 mmole; 45 percent recovery) and 2,2,3,4,4,4- hexafluorobutylmethyl ether (2.08 g., 10,61 mmole; 65 percent yield based on C Fconsumed) (Found: C, 31.6; H, 3.1 percent; M, 194. C H F O requires C,30.6; H, 3.1 percent; M, 196), b.p. 87/758 mm.

We claim:

1. A process for inserting hexafluoropropene into the structure of ahydrocarbon compound or substituted hydrocarbon compound containing atleast one aliphatic carbon-hydrogen bond and which is free of acetylenicand terminal ethylenic unsaturation, said insertion of hexafluoropropenebeing at said carbonhydrogen bond, which comprises contacting at atemperature within the range of about 20C. to about 150C. saidhydrocarbon compound with hexafluoropropene monomer while exposed toultra violet light radiation, in the absence of free oxygen-containinggases and free-radical catalyst.

2. A process according to claim 1 wherein the temperature is in therange of about 30C to C.

3. A process according to claim 1 wherein the molar ratio ofhexafluoropropene to the hydrocarbon reactant is in the range of 2:1 to4:1.

2. A process according to claim 1 wherein the temperature is in the range of about 30*C to 100*C.
 3. A process according to claim 1 wherein the molar ratio of hexafluoropropene to the hydrocarbon reactant is in the range of 2:1 to 4:1. 